US4578524A - Carbon dioxide-enhanced monoalkylene glycol production - Google Patents

Carbon dioxide-enhanced monoalkylene glycol production Download PDF

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US4578524A
US4578524A US06/594,265 US59426584A US4578524A US 4578524 A US4578524 A US 4578524A US 59426584 A US59426584 A US 59426584A US 4578524 A US4578524 A US 4578524A
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vanadate
carbon dioxide
metavanadate
orthovanadate
reaction
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Brian T. Keen
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Union Carbide Corp
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Union Carbide Corp
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Assigned to UNION CARBIDE CORPORATION, OLD RIDGEBURY ROAD, DANBURY, CT. 06817 A NY CORP. reassignment UNION CARBIDE CORPORATION, OLD RIDGEBURY ROAD, DANBURY, CT. 06817 A NY CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KEEN, BRIAN T.
Priority to EP85200479A priority patent/EP0156447A3/en
Priority to JP60062240A priority patent/JPS60222432A/ja
Priority to CA000477830A priority patent/CA1248144A/en
Assigned to MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. reassignment MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: STP CORPORATION, A CORP. OF DE.,, UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,, UNION CARBIDE CORPORATION, A CORP.,, UNION CARBIDE EUROPE S.A., A SWISS CORP.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to processes for the hydrolysis of vicinal alkylene oxides to the corresponding alkylene glycols in the presence of vanadate anion in a liquid menstruum and in the presence of a selectivity-enhancing amont of carbon dioxide.
  • Alkylene oxides for example, ethylene oxide, propylene oxide and butylene oxide
  • ethylene oxide, propylene oxide and butylene oxide have been subjected to liquid-phase hydration to produce the corresponding alkylene glycols.
  • ethylene glycol from ethylene oxide
  • large molar excesses of water are used (See, Kirk-Othmer, Encyclopedia of Chemical Technology Volume 11, Third Edition, Page 939, (1980)). It has been reported that the presence of large quantities of water in the reaction system are necessary if the yield to the desired monoalkylene glycol is to be great enough to be commercially viable and minimize the production of by-products such as diglycols and triglycols. Accordingly, the commercial practice has generally involved the hydration of an alkylene oxide at a temperature of about 100° C.
  • the selectivity of the hydration process to monoglycol e.g., ethylene glycol, propylene glycol or butylene glycol
  • any process which would favorably decrease the relative amount of water employed to alkylene oxide hydrated while not increasing, or preferably decreasing, the by-products formed would be advantageous.
  • the energy and equipment requirements would necessarily be less for separation and purification processes relating to the removal and recovery of the monoglycol from water and by-products.
  • catalysts have been suggested for use in the hydration of alkylene oxides, including the use of acid catalysts such as: alkyl sulfonic acid ion exchange resins (U.S. Pat. No. 4,165,440); carboxylic acids and halogen acids (U.S. Pat. No. 4,112,054); strong acid cation exchange resins (U.S. Pat. No. 4,107,221); aliphatic monocarboxylic and/or polycarboxylic acids (U.S. Pat. No. 3,933,923); cationic exchange resins (U.S. Pat. No. 3,062,889); acidic zeolites (U.S. Pat. No. 3,028,434); sulfur dioxide (U.S. Pat.
  • acid catalysts such as: alkyl sulfonic acid ion exchange resins (U.S. Pat. No. 4,165,440); carboxylic acids and halogen acids (U.S. Pat. No. 4,112,054); strong acid c
  • alkali metal halides such as chlorides, bromides and iodides, quaternary ammonium halides such as tetramethyl ammonium iodide and tetramethyl ammonium bromide
  • quaternary ammonium halides such as tetramethyl ammonium iodide and tetramethyl ammonium bromide
  • organic tertiary amines such as triethylamine and pyridine (German published patent application No. 2,615,595, Oct. 14, 1976, and U.S. Pat. No. 4,307,256, issued Dec. 22, 1981); quaternary phosphonium salts (U.S. Pat. No.
  • tertiary amines have certain chemical and physical properties which prevent their ready use as hydration catalysts.
  • tertiary amines have a strong pungent odor which is not desirable in manufacturing and can detract from the quality of the end product.
  • U.S. Pat. No. 4,277,632, issued July 7, 1981 discloses a process for the production of alkylene glycols by the hydrolysis of alkylene oxides in the presence of a catalyst of at least one member selected from the group consisting of molybdenum and tungsten.
  • the catalyst may be metallic molybdenum or metallic tungsten, or inorganic or organic compounds thereof, such as oxides, acids, halides, phosphorous compounds, polyacids, alkali metal and alkaline earth metal, ammonium salts and heavy metal salts of acids and polyacids, and organic acid salts.
  • An objective of the disclosed process is stated to be the hydrolysis of alkylene oxides wherein water is present in about one to five times the stoichiometric value without forming the appreciable amounts of by-products, such as the polyglycols.
  • the reaction may be carried out in the presence of carbon dioxide.
  • the patentees state that the process can be effectively carried out in the presence of from 0.00001 to 1, preferably from 0.0001 to 1, mole of carbon dioxide per mole of alkylene oxide. In the examples, where carbon dioxide was employed (either as carbon dioxide or a bicarbonate salt), the amount ranged from 0.001 to 0.08 mole of carbon dioxide per mole of ethylene oxide.
  • Japanese Kokai No. JA 54/128,507 published Oct. 5, 1979, discloses a process for the production of alkylene glycols from alkylene oxides and water using metallic tungsten and/or tungsten compounds.
  • Japanese Kokai No. JA 56/073,036, published June 17, 1981, discloses a process for the hydrolysis of alkylene oxide under a carbon dioxide atmosphere in the presence of a catalyst consisting of a compound containing at least one element selected from a group comprising aluminum, silicon, germanium, tin, lead, iron, cobalt and nickel.
  • Japanese Kokai No. JA 56/073,035, published June 17, 1981, discloses a process for the hydrolysis of alkylene oxide under a carbon dioxide atmosphere in the presence of a catalyst consisting of a compound containing at least one element selected from the group of titanium, zirconium, vanadium, niobium, tantalum and chromium.
  • the amount of carbon dioxide to be employed in the disclosed process is within the range of 0.00001 to 1, preferably, 0.0001 to 1, mole of carbon dioxide per mole of alkylene oxide.
  • the compounds employed as the catalysts include the oxides, sulfides, acids, halides, phosphorous compounds, polyacids, alkali metal salts of acids and polyacids, ammonium salts of acids and polyacids, and heavy metal salts of acids.
  • the examples show the use of various metal catalysts, the disclosure does not disclose any detail as to the nature of the hydration process and the selection of the catalysts employed therein.
  • the process is carried out using a potassium vanadate as the hydration catalyst for the production of ethylene glycol from ethylene oxide and water under a carbon dioxide pressure. No identification of the vanadate used was made. The carbon dioxide was provided in the amount of 0.01 mole per mole of ethylene oxide.
  • Japanese Kokai No. JA 56/92228, published July 25, 1981, is directed to processes for producing highly pure alkylene glycols.
  • the disclosure is directed to a distillation procedure for recovery of a molybdenum and/or tungsten-containing catalyst from an alkylene oxide hydrolysis process in the presence of carbon dioxide.
  • the catalyst is at least one compound selected from the group consisting of compounds of molybdenum and tungsten which compound may be in combination with at least one additive selected from the group consisting of compounds of alkali metals, compounds of alkaline earth metals, quaternary ammonium salts and quaternary phosphonium salts.
  • the preferred catalysts are stated to be molybdic acid, sodium molybdate, potassium molybdate, tungstic acid, sodium tungstate and potassium tungstate. Potassium iodide is the only additive employed in the examples.
  • J. H. Robson and G. E. Keller, II in copending U.S. patent application Ser. No. 530,235, filed Sept. 8, 1983, herein incorporated by reference, disclose the use of water-soluble vanadate salts at a pH of between 5 and 12 to enhance the selectivity of the hydration of alkylene oxides to monoalkylene glycols.
  • One preferred vanadate salt comprises metavanadate, and it is reported that carbon dioxide decreases the selectivity to the monoalkylene glycol product when using this salt.
  • carbon dioxide is disclosed to be desirably less than about 0.10, preferably less than 0.05, mole per mole of alkylene oxide.
  • This invention relates to processes for the production of the corresponding monoalkylene glycol by the hydration in a liquid phase of alkylene oxide in the presence of vanadate anion and in the presence of a selectivity-enhancing amount of carbon dioxide.
  • the amount of carbon dioxide that provides the enhancing effect falls within a narrow range as set forth below and is believed to be dependent upon the vanadate species present.
  • the processes of this invention provide enhanced selectivity to monoalkylene glycol.
  • the selectivities achievable using this invention are greater than those obtained under common conditions including using vanadate anion but not using the amounts of carbon dioxide in accordance with the invention.
  • This invention relates to processes for the production of monoalkylene glycols by the reaction of water with vicinal alkylene oxide having the general formula ##STR1## wherein R 1 , R 2 , R 3 and R 4 each designate a hydrogen atom, an alkyl group having between 1 and about 10 carbon atoms, an aryl group having at least 6 carbon atoms (e.g., monocyclic or bicyclic aryl), an alkenyl group having 2 or 3 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 each designate a hydrogen atom, an alkyl group having between 1 and about 10 carbon atoms, an aryl group having at least 6 carbon atoms (e.g., monocyclic or bicyclic aryl), an alkenyl group having 2 or 3 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
  • alkylene oxides which may be employed in the instant invention are ethylene oxide, propylene oxide, butylene oxide (including isobutylene oxide, 1,2-butylene oxide and 2,3-butylene oxide), pentylene oxide, cyclohexene oxide, styrene oxide, and the like.
  • the alkylene oxide is an aliphatic alkylene oxide such as ethylene oxide and propylene oxide.
  • alkylene oxide formed by most any process may be employed in the instant invention.
  • ethylene oxide is the selected alkylene oxide it may be formed by the catalytic oxidation of ethylene with molecular oxygen or an oxygen-containing gas in the presence of a silver catalyst.
  • Such a process for forming the ethylene oxide employed herein is particularly desirable since substantially pure ethylene oxide may be obtained.
  • the process also employs water as a reagent for the formation of the corresponding alkylene glycol.
  • the source of the water is not important. Demineralized water obtained by, for example, ion exchange treatment, or other water of sufficient purity is usable in hydration processes.
  • the amount of water to be used, relative to a mole of alkylene oxide is generally between about 1 and about 40 moles, preferably up to about 30 moles, say, between about 1 and 30 moles and preferably between about 1 and 20 moles, and about 1 to about 10 moles if reducing energy and equipment costs for glycol-water separation is a primary objective.
  • the molar ratio of water required for hydrolysis to alkylene oxide may be decreased below about 5 moles of water per mole of alkylene oxide, it is generally desirable to maintain at least a slight molar excess of water over the stoichiometric amount of water to ensure a higher selectivity of alkylene oxide to the monoalkylene glycol product.
  • molar ratio of water to alkylene oxide i.e., molar hydrolysis ratio
  • commercially-attractive selectivities to monoalkylene glycol can be obtained, e.g., greater than about 70, say, greater than about 80, percent (mole basis).
  • Vanadate chemistry is complex and numerous vanadate anions species, e.g., metavanadate, hydrogen pyrovanadate, pyrovanadate and orthovanadate anions, have been identified although their specific structures are not fully known. For purposes of discussion, common structural reference to these anions is as follows: metavanadate, (VO 3 ) - ; hydrogen pyrovanadate (HV 2 O 7 ) 3- ; pyrovanadate, (V 2 O 7 ) 4- ; and orthovanadate, (VO 4 ) 3- .
  • vanadate species present is thought to be dependent on the pH of the liquid phase. Hence, at a pH of, say, about 12, little, if any, metavanadate anion may exist. Although the processes are carried out by providing a water-soluble vanadate salt to the reaction system, the exact nature of the catalytic species is not fully known.
  • the vanadate anion can be characterized in terms of a mixture of metavanadate and orthovanadate, that is, a calculated mole ratio of these two anions.
  • pyrovanadate can be expressed as a mixture of one mole of metavanadate and one mole of orthovanadate; i.e., VO 3 - +VO 4 3- equals V 2 O 7 4-
  • hydrogen pyrovanadate can be expressed as the mole ratio of metavanadate to orthovanadate of 3:1.
  • the calculated mole ratio of metavanadate to orthovanadate for the vanadate anion useful in accordance with this invention is less than 2.2:1, and is often in the range of about 0.001:1 to 2.0:1, preferably about 0.1:1 to 1.5:1.
  • the calculated mole ratio of metavanadate to orthovanadate is determined prior to the addition of carbon dioxide.
  • the calculated mole ratio may be determined from an analysis of the vanadate species in the reaction medium, e.g., by nuclear magnetic resonance spectroscopy, and then calculating the amounts of metavanadate and orthovanadate required to provide the concentrations of the observed vanadates.
  • the ratio may be determined directly from using metavanadate and orthovanadate as the adjuvants. If the latter method is employed, it should be recognized that the addition of an acid or base could change the mole ratio of metavanadate to orthovanadate.
  • the cation to the vanadate anion will permit the vanadate anion to become dissociated in water. While cations which provide water soluble vanadate-containing compounds, under reaction conditions, such as the alkali metal salts, quaternary ammonium salts, ammonium salts, and the like, are useful, cations which are substantially insoluble, or have little solubility, in water at reaction conditions can be used providing that the vanadate anion is able to interact with the alkylene oxide. This activity is believed to exist when the vanadate anion is capable of being dissociated from the cation. Thus, calcium vanadate, which has little solubility in water and retains the vanadate anion tightly bound, has not been found to be an acceptable vanadate-containing compound. On the other hand, where the cation is an essentially insoluble quaternary ammonium moiety, the dissociatable nature of the vanadate anion is believed to permit its usefulness in accordance with the invention.
  • suitable cations may include structures represented by the formulae: ##STR2## where Y is nitrogen, phosphorous, or arsenic (formula A), or sulfur (formula B), i.e., ammoniums, phosphoniums, arsoniums and sulfoniums, where each of R 5 , R 6 , R 7 and R 8 may be the same or different and may combine to form cyclic structures.
  • exemplary of each of R 5 , R 6 , R 7 and R 8 are hydrogen and unsubstituted and substituted hydrocarbyls of 1 or more carbon atoms, e.g., to about 70 carbon atoms. Representative cations are disclosed in copending U.S. patent application Ser. No.
  • R 5 ,264 filed on even date herewith, of J. R. Issuegs and J. H. Robson, herein incorporated by reference.
  • At least one of R 5 , R 6 , R 7 and R 8 may be bonded or complexed to an organic or inorganic solid.
  • anion exchange resins are disclosed which have electropositive complexing sites which, among other possibilities, can be quaternary ammonium or quaternary phosphonium moieties that are in association with the vanadate anion.
  • Other organic-containing cations which may be useful include the bis(hydrocarbyl-phosphine)iminiums represented by the formula
  • each R 9 may be the same or different and maybe the same as set forth for R 5 to R 8 .
  • Illustrative iminiums are disclosed in Ser. No. 594,264.
  • the vanadate anion may be provided to the reaction mixture as a vanadate anion or in a form which is converted to the desired vanadate anion by subsequent chemical reaction.
  • halide, sulfide, or the like, vanadium-containing compounds may be employed as the precursor to the desired vanadate anion. Some of these precursor compounds may be converted to vanadates during the hydration reaction.
  • the vanadate may be used in the salt form or may be introduced into the reaction system on a support, such as on a carrier such as silica, alumina, zeolites, clay, and the like.
  • a carrier such as silica, alumina, zeolites, clay, and the like.
  • the vanadate is generally in a dissolved, mixed, suspended, or deposited form in a fixed bed in the liquid phase with the reactants, i.e., the alkylene oxide and water.
  • the vanadate may be provided to the reaction system by mixing it with water being introduced into the reaction system, it may be introduced by means of a separate inlet to the reaction system, or it may be retained in the reaction zone as an immiscible organic phase or solid phase.
  • the vanadate-containing adjuvant is water-soluble, replenishing the reaction zone is desired.
  • the exact means of introduction of the vanadate is not critical, and frequently the vanadate is provided at the beginning of the reaction and/or is continuously or intermittently added
  • the vanadate salt (calculated as metavanadate anion regardless of the form of the vanadate anion added to, or present in, the reaction system) is generally provided in an amount sufficient to enhance selectivity, e.g., at least 0.005 percent, based on the weight of the vicinal alkylene oxide employed, and is preferably employed in an amount between about 0.01 and about 90 percent by weight, and most preferably between about 0.05 and about 30 percent by weight, based on the weight of the alkylene oxide employed.
  • the selectivity enhancement provided by carbon dioxide is achieved when employing certain ratios of carbon dioxide to vanadate anion.
  • the amount of carbon dioxide provided per mole of vanadium atoms present is typically from about (a) 0.5-M/O to (b) 2.2-M/O, wherein M/O is the calculated mole ratio of metavanadate to orthovanadate with the proviso that at least 0.01 mole of carbon dioxide is provided per mole of vanadium atoms.
  • the mole ratio of carbon dioxide to vanadium atoms is in the range of about (a) 0.5-M/O to (b) 1.9-M/O, say, about (a) 0.7-M/O to (b) 1.8-M/O.
  • the mole ratio of carbon dioxide atoms to vanadium atoms is in the range of about (a) 0.75-M/O to (b) 1.5-M/O.
  • the amount of carbon dioxide provided in accordance with this invention should be adjusted accordingly.
  • the carbon dioxide may be provided to the reaction zone in any convenient manner.
  • the carbon dioxide may, for instance, be introduced separately and/or with one or more of the feed streams.
  • carbon dioxide is generated.
  • some carbon dioxide is provided to the reaction system.
  • the carbon dioxide present in the alkylene oxide feed stream is greater than that desired in the reaction zone, it may be flashed from the alkylene oxide or removed in another suitable manner.
  • the carbon dioxide is relatively uniformly dispersed in the reaction medium.
  • At least a portion of the carbon dioxide may be added in other than that molecular form.
  • water soluble bicarbonate e.g., as the alkali metal, alkaline earth metal, ammonium, etc., salts, or carbonic acid may provide a portion of the carbon dioxide.
  • these species can affect the form of the vanadate.
  • the calculated mole ratio of metavanadate to orthovanadate may be increased.
  • a mixture of two moles of metavanadate and two moles of bicarbonate may provide the same performance as obtained using a vanadate having a calculated mole ratio of metavanadate to orthovanadate of 1:1 and one mole of carbon dioxide per mole of vanadium atoms.
  • alkylene glycol is effectively carried out in the presence of a gas, such as air, argon, nitrogen, and the like, as a diluent for the reaction system.
  • a gas such as air, argon, nitrogen, and the like
  • the pH of the reaction system can affect the rate and, importantly, selectivity to monoalkylene glycol. Although the exact relationship of selectivity and pH is not yet known, it is believed that, for instance, a metavanadate anion may undergo in situ modification to provide the active species of vanadium or vanadate which provides the advantageous selectivities to monoethylene glycol.
  • the initial pH of the reaction system is between about 5 and about 12, e.g., about 7 to 11, and preferably, the pH is within the ranges during the process. It is believed that the pH should be between about 8.5 and about 10.5, say, about 9.2 to 10.5, and sometimes between about 9.6 and 10.3.
  • the pH may be affected by a number of mechanisms including the presence of carbon dioxide.
  • acid or base such as sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, alkali metal hydroxide (e.g., sodium hydroxide and potassium hydroxide), ammonium hydroxide and the like may be added.
  • an adjuvant which is used to modify the pH, does not result in precipitation of the vanadate or does not otherwise untowardly affect the reaction system or products.
  • the pH is affected by the vanadate anion added and its concentration.
  • orthovanadate is strongly basic and may be used in combination with metavanadate or pyrovanadate as a means to adjust the pH.
  • concentration of vanadate anion will affect the pH. It is believed, however, that carbon dioxide provides a greater enhancement of selectivity than that provided by an initial pH adjustment.
  • the process is usually carried out at a temperature between about 20° C. and about 250° C., preferably between about 50° C. and about 200° C. Temperatures above 250° C. may be employed depending on the selection of the alkylene oxide, vanadate salt compound and pressure employed; however, such high temperatures are not generally preferred.
  • the process is typically carried out at a pressure in the range between about 0 kg/cm 2 G and about 1000 kg/cm 2 G and preferably between about 2 kg/cm 2 G and about 100 kg/cm 2 G, although pressures outside these preferred ranges are believed to be operable.
  • the process of this invention can be operated in the presence of a water-miscible solvent which may serve to dilute the reaction mixtue.
  • a water-miscible solvent which may serve to dilute the reaction mixtue.
  • Any liquid which at the reaction temperature is totally miscible with the alkylene oxide water and the glycol product(s) can be a solvent, provided that it is not reactive with either the alkylene oxide reactant, the alkylene glycol produced or the vanadate salt employed.
  • compounds such as carboxylic acid, phenols, aldehydes and alkylene carbonates are preferably not employed as solvents in the practice of this invention.
  • the alkylene glycol product is often a very good solvent. If an alkylene glycol is employed as a solvent, preferably it is the same as the alkylene glycol product.
  • the solvents are useful for the purpose of controlling reaction temperature (particularly at low hydrolysis ratios) and rate and are useful in recycle systems in continuous processes.
  • the processes of this invention may be carried out as a batch reaction or as a continuous process.
  • Conventional autoclaves can be employed when using elevated temperatures, but glassware-type equipment can be used when operated at moderate pressures.
  • Plug-flow reactors are often utilized in conventional continuous procedures. Solvent may be recycled and catalyst may be recovered.
  • the reaction may be carried out for very short periods of time, e.g., fractions of a second, and, if desired, may be carried out over reaction periods of up to hours.
  • the process conditions are governed by the amounts of solvent and catalyst employed, the pressures and temperatures employed, and like considerations.
  • the alkylene oxide is ethylene oxide
  • the selectivity to monoethylene glycol over diethylene glycol and triethylene glycol is greater than 70 molar percent and generally greater than 80 molar percent.
  • the combinations of hydrolysis ratio, vanadate concentration, carbon dioxide concentration and pH can be correlated to provide optional results for a particular objective.
  • the objective is to provide high selectivity to monoalkylene glycol, higher hydrolysis ratios may be employed, and selectivities of greater than 95 percent at 20:1 molar hydrolysis ratios may be achievable.
  • the objective is to use low hyrolysis ratios to reduce the costs associated with the glycol-water separation, the comparable selectivities to those obtained in conventional hydrolysis operations may be achievable at low hydrolysis ratios. For example, selectivities of greater than 90 percent can be obtained at molar hydrolysis ratios of around 5:1.
  • TM 1,3-butanediol
  • BSTFA N,N-bistrimethylsilyl trifluoroacetamide
  • the weight percent monoethylene glycol, diethylene glycol and triethylene glycol are determined by standard vapor phase chromatography using a Hewlett Packard 5880 (TM) gas chromatograph equipped with a four meter by 1/8 inch (0.32 centimeters) (outside diameter) stainless steel column packed with 20 percent OV-101 methylsilicone stationary liquid phase supported on 80/100 mesh Chromosorb W HP (TM) both available from Supelco, Inc. Bellefonte, Pa.
  • the selectivity to each glycol component is calculated as the quotient of the weight percent of the subject glycol divided by the sum of the weight percents of each of the monoethylene glycol, diethylene glycol and triethylene glycol.
  • Ethylene oxide and water stock solution were prepared in chilled (about 5° C.) 120 cubic centimeter serum bottles as follows:
  • Solution A 75.0 g H 2 O and 25.0 g ethylene oxide.
  • Solution B 70.0 g H 2 O and 10.0 g ethylene oxide.
  • Solution C 75.0 g H 2 O (saturated with CO 2 ) and 25.0 g ethylene oxide.
  • Solution D 70.0 g H 2 O (saturated with CO 2 ) and 10.0 g ethylene oxide.
  • Solution E 75.0 g H 2 O (pH 4 by H 2 SO 4 as a 1% aqueous solution) and 25.0 g ethylene oxide.
  • Solution F 70.0 g H 2 O (pH 4 by H 2 SO 4 as a 1% aqueous solution) and 10.0 g ethylene oxide.
  • Solutions C and D had an approximate pH of 4.

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US06/594,265 US4578524A (en) 1984-03-28 1984-03-28 Carbon dioxide-enhanced monoalkylene glycol production
EP85200479A EP0156447A3 (en) 1984-03-28 1985-03-28 Carbon dioxide-enhanced monoalkylene glycol production
JP60062240A JPS60222432A (ja) 1984-03-28 1985-03-28 二酸化炭素により選択性を高めたモノアルキレングリコールの製造方法
CA000477830A CA1248144A (en) 1984-03-28 1985-03-28 Carbon dioxide enhanced monoalkylene glycol production

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* Cited by examiner, † Cited by third party
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US4967018A (en) * 1987-11-25 1990-10-30 Union Carbide Chemicals And Plastics Company Inc. Monoalkylene glycol production using mixed metal framework compositions
CN103987685A (zh) * 2011-12-13 2014-08-13 住友化学株式会社 由环氧乙烷化合物制造二醇类的方法

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RU2122995C1 (ru) * 1997-09-09 1998-12-10 Швец Валерий Федорович Способ получения алкиленгликолей
US7459589B2 (en) 2005-12-22 2008-12-02 Shell Oil Company Process for the preparation of an alkylene glycol
US7704908B2 (en) 2005-12-22 2010-04-27 Shell Oil Company Method for reusing rhenium from a donor spent epoxidation catalyst

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
US4701571A (en) * 1986-06-30 1987-10-20 Union Carbide Corporation Process for the production of alkylene glycols with metalate-containing solids
US4967018A (en) * 1987-11-25 1990-10-30 Union Carbide Chemicals And Plastics Company Inc. Monoalkylene glycol production using mixed metal framework compositions
US5064804A (en) * 1987-11-25 1991-11-12 Union Carbide Chemicals And Plastics Technology Corporation Mixed metal framework compositions for monoalkylene glycol production
CN103987685A (zh) * 2011-12-13 2014-08-13 住友化学株式会社 由环氧乙烷化合物制造二醇类的方法
CN103987685B (zh) * 2011-12-13 2015-11-25 住友化学株式会社 由环氧乙烷化合物制造二醇类的方法
US9828318B2 (en) 2011-12-13 2017-11-28 Sumitomo Chemical Company, Limited Method for producing glycols from oxirane compounds

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JPH0536421B2 (enrdf_load_stackoverflow) 1993-05-31
EP0156447A3 (en) 1987-02-04
JPS60222432A (ja) 1985-11-07
CA1248144A (en) 1989-01-03
EP0156447A2 (en) 1985-10-02

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